JPS61156145A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain a toner giving necessary image density, having fog resis tance, and not attaching to a soft polyvinyl chloride sheet by incorporating as a binder at least one of polymerizable unsatd. monomers represented by formula I-V. CONSTITUTION:The electrostatic charge image developing toner contains in an amt. of 10-90wt% at least one of polymerizable unsated. monomers represented by formula I-V in which R1 is H or methyl; R2 is 1-6C alkylene; each of R3-R10 is H, 1-3C alkyl or halogen, independent of each other; and R11 is -CH2- or the like. When an amt. of a specified monomer to be mixed is too much, the performance as the toner becomes insufficient.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a toner for developing electrostatic images used in fields such as electrophotography and electrostatic recording.

(Prior Art) In electrophotography and electrostatic recording, an electrostatic charge image is formed on a photoreceptor by various methods, and then the electrostatic charge image is developed with toner particles. A printed matter is obtained by transferring the image to another transfer material such as a Mylar film and fixing it with a heated roll, a pressure roll, a heated pressure roll, or 7-lash light from a xenon lamp.

Prints are often kept in paper containers made of soft vinyl chloride polymer sheets to prevent stains and damage and for long-term use or storage.

Toners for developing electrostatic images used in the fields of electrophotography and electrostatic recording include toners using polystyrene resin (Japanese Patent Publication No. 44-16118) and toners using methylene-butyl methacrylate copolymer resin. (Tokuko Showa 56-1
Toners using vinyl resins such as (Japanese Patent Application Laid-Open No. 1143), toners using bisphenol-type epoxy resins obtained by reacting bisphenol and epichlorohydrin (Japanese Patent Application Laid-Open No. 1983-96354), glycols having a bisphenol skeleton and polybasic Toner using polyester resin obtained by reacting with acid (Japanese Patent Publication No. 52-25420)
Publication No.) etc. are known.

Compared to other resins, the physical properties of vinyl resins, such as molecular weight, glass transition point, and melt viscosity, can be controlled over a wide range, which is extremely advantageous in toner design, so most toners are made using vinyl resins. occupied by toner.

(Problems to be Solved by the Invention) By the way, in order to prevent stains and damage and to use or store the printed matter for a long time, printed matter is often kept in a paper case made of a soft vinyl chloride polymer sheet. However, with conventional toners using vinyl resin, when printed matter made with the toner is sandwiched between soft PVC polymer sheets, the printed characters and figures adhere to the sheets, causing print defects and making it difficult to read. It had the serious drawback of becoming incapacitated.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide a toner that has the necessary image density and fog resistance as a toner and does not adhere to a soft vinyl chloride polymer sheet.

(Means for Solving the Problems) The present invention uses at least one kind of polymerizable unsaturated monomers represented by any of the following general formulas I to
The present invention relates to a toner for developing electrostatic images, which contains a polymer containing up to 90% by weight as a binder.

Rs, R4, 几s, R11y R7, R11, R9 and RIO are hydrogen.

It is an alkyl group having 1 to 3 carbon atoms or a halogen.

These may be the same or different. 7H'' -CH2CH-] The binder for the electrostatic image developing toner according to the present invention is as follows.

A monomer containing at least one kind of polymerizable unsaturated monomer represented by any of the above general formulas 1-V (hereinafter referred to as "specific monomer of the present invention") is required as a component. The following agents are used:

(B) Copolymer of at least one specific monomer of the present invention and another polymerizable unsaturated monomer (A)
A mixture of a copolymer of the present invention and another resin (C1 A copolymer of one of the specific monomers of the present invention and/or a copolymer of two or more of the specific monomers of the present invention and the above (A) Coalescence and/or mixture with other resins At least one of the specific monomers of the present invention is contained in the binder in an amount of 10 to 90% by weight, preferably 20 to 70% by weight, particularly preferably 30 to 60% by weight. It is blended to have a heavy weight content.

If the amount of the specific monomer of the present invention is too small, the adhesion resistance of the toner to the vinyl chloride polymer will be insufficient, and if it is too large, the performance as a toner will be insufficient.

The specific monomer of the present invention may be prepared by imidizing an acid anhydride having a corresponding alicyclic structure with an amino alcohol having 1 to 6 carbon atoms, and then adding acrylic acid or methacrylic acid or a lower alkyl ester thereof. It can be produced by carrying out an esterification reaction or a transesterification reaction.

Typical examples include secondary monomers AG.

Furthermore, primary monomers can be used as the other polymerizable unsaturated monomers.

(Nostyrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, and p-chlorostyrene.

(bl methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate,
Heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, methacrylic acid Ethoxydiethylene glycol, methoxyethylene glycol methacrylate, butoxytriethylene glycol methacrylate, methoxydiglopine/glycol methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, methacrylate Tetrahydrofurfuryl acid, dicyclopentenyl methacrylate.

Dicyclopentenyloxyethyl methacrylate.

N-vinyl-2-pyrrolidone methacrylate, methacrylonitrile, methacrylamide, N-methylolmethacrylamide, 2-hydroxyethyl methacrylate, hydroxyglobil methacrylate.

Hydroxybutyl methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate.

(C) Diacetone acrylamide, acrylic acid.

Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate.

Octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate,
Methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate.
Phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl 7-IJ chloride, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, acrylic acid N-vinyl-2-
Pyrrolidone, hydroxyethyl acrylate, hydroxyglobil acrylate, hydroxybutyl acrylate.

2-hydroxy-3-phenyloxypropyl acrylate, glycidyl acrylate, acrylonitrile, acrylamide, N-methylolacrylamide, diacetone acrylamide, vinylpyridine.

(d+ General formula [In formula 2, 几- is hydrogen or methyl group, X is -O-
, -N- or -8-, R≦ is CnHzn (n is I~
(an integer of 20) and R3 are morpholinomethyl acrylate, morpholinoethyl acrylate, 2-morpholinopropyl acrylate,
3-morpholinopropyl acrylate, 2-morpholinopropyl acrylate, 4-morpholinobutyl acrylate, 3-morpholinobutyl acrylate, 2-morpholinobutyl acrylate, 2-morpholinopentyl acrylate.

Morpholinoalkyl acrylates such as 2-morpholinohexyl acrylate and 2-morpholinooctyl acrylate, methacrylates having morpholinoalkyl similar to these, and morpholinoalkyl acrylates such as those exemplified above, in which aziridyl or piperazyl groups are substituted for the morpholino group. or aziridyl alkyl acrylate, piperidyl alkyl acrylate and piperidyl alkyl acrylate to which a piperidyl group is bonded;
Aziridyl alkyl methacrylate, piperadylalkyl methacrylate and piperidyl alkyl acrylate, morpholinomethyl acrylamide, morpholinoethyl acrylamide, 3 having alkyl groups similar to these
-morpholinopropylacrylamide, 2-morpholinopropylacrylamide, 4-morpholinobutylacrylamide, 3-morpholinobutylacrylamide, 2-
Morpholinoalkylacrylamide such as morpholinobutylacrylamide, 2-morpholinopentylalkyl acrylamide, 2-morpholinohexylacrylamide, 2-morpholinooctylacrylamide, morpholinoalkyl methacrylate having a morpholinoalkyl group similar to these, morpholinoalkyl as exemplified above. An aziridyl alkyl acrylate in which an aziridine group, a piperazyl group, or a piperidyl group is bonded in place of one morpholino group in the acrylate.

Piperazyl alkyl acrylate and piperidyl
゛Alkyl acrylate, aziridyl alkyl methacrylate having an alkyl group similar to these.

Piperadyl alkyl methacrylate and piperidyl alkyl methacrylate, morpholinomethylthioacrylate, morpholinoethylthioacrylate, 3-morpholinopropylthioacrylate.

Morpholinos such as 2-morpholinopropylthioacrylate, 4-morpholinobutylthioacrylate, 3-morpholinobutylthioacrylate, 2-morpholinoptylthioacrylate, 2-morpholinopentylthioacrylate, 2-morpholinohexylthioacrylate, 2-morpholinooctyl acrylate Alkylthioacrylate.

Morpholinoalkylthiomethacrylates having a morpholinoalkyl group similar to these, aziridylalkylthioacrylates in which an aziridyl group, piperazyl group or piperidyl group is bonded in place of one morpholino group in the morpholinoalkylthioacrylates exemplified above; There are radilalkylthioacrylates and piperidylalkylthioacrylates, aziridylalkylthiomethacrylates, piperidylalkylthiomethacrylates and piperidylalkylthiomethacrylates having similar alkyl groups. Furthermore, as a monomer containing a cyclic amino group.

N-vinylpyrrole, N-vinylcarbazole.

N- such as N-vinylindole and N-vinylpyrrolidone
There are vinyl compounds.

(e) Acyclic amino group-containing polymerizable monomer: Specifically, α-methylene such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, dimethylaminomethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, etc. Aliphatic monocarboxylic acid aminoalkyl ester.

(f) Divinylbenzene, reaction products of glycol and methacrylic acid or acrylic acid 2 such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-bentanediol dimethacrylate methacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate.

Tripropylene glycol dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, trimethylolethane trimethacrylate,
Trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, trismethacryloxyethyl phosphate.

Bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, tris(methacryloyloxyethyl)in cyanurate, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1
．． 4-butanediol diacrylate, 1,5-bentanediol diacrylate, 1,6-hexanediol diacrylate.

Neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate,
Tripropylene diacrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate.

Pentaerythritol tetraacrylate, trisacryloxyethyl phosphate, bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, tris(methacryloyloxyethyl)in cyanurate, halfester compound of glycidyl methacrylate and methacrylic acid or acrylic acid, bisphenol type epoxy resin and halfesterization of methacrylic acid or acrylic acid.

Among these other polymerizable unsaturated monomers, preferred are those having one vinyl group in one molecule, such as styrene, styrene, etc. derivatives, methacrylic esters,
Acrylic acid ester, etc. 2% alkyl group 1-5
Preferred are alkyl esters of methacrylic acid or acrylic acid having 5 carbon atoms.

Polymerizable unsaturated monomers having two or more vinyl groups in one molecule as shown in (f)K above include divinylbenzene,
Dimethacrylates and diacrylates of methylene glycol having 2 to 6 carbon atoms are preferred, and these are used in an amount of 0 to 20% by weight based on the total polymerizable unsaturated monomers.

Examples of the other resins include polymers of the other polymerizable unsaturated monomers, KRl-216, KR-220, KR-15.
2, Ni-271, KR-255 (Shin-Etsu Chemical Co., Ltd.)
Itri, 5R-2400, 5R-2406, 5H-84
Silicone resin such as 0 (made of silicone),
Or 1-flex (manufactured by CdF chemical)
norbornene polymer, or C-20OA, C-
25OA (manufactured by Mitsubishi Chemical Industries, Ltd.).

Polyester carbonate such as Kneepilon P-1000 (manufactured by Mitsubishi Gas Chemical), or Gnorr R-70
, R, 120, R-140, P-2 (more than lignite ■
Xylene resin such as
,1007,1009,1010゜YL-903,90
6. Epoxy resins such as Epicoat 604 (manufactured by Shell), EvoMitsuku R304, R307, R309 (Mitsui Petrochemical Industries ■ size), or Nirapol BR-
1220, 1032° 1441, Nilaball rR220
0, Diene resin such as Nilaball NBR, 20578, 2007J (manufactured by Nippon Zeon), or PC
-RESIN2H, 3H, 8H, IIA (manufactured by Hitachi Chemical Co., Ltd.).

There are polyester resins such as ATR2005, 2009, and 2010 (manufactured by Kao Soap), phenol resins, Cuman resins, amide resins, amide imide resins, butyral resins, amine resins, urethane resins, etc. It is added in an amount of 30% by weight.

It is particularly preferable that the binder of the present invention has a glass transition temperature adjusted to 20 to 100°C. Glass transition temperature is 20℃
If it is less than 100%, the toner tends to cause caking (a phenomenon in which toner particles aggregate to form lumps) during storage or in developing machines such as printers and copiers. Further, when the glass transition temperature exceeds 100° C., when the toner is manufactured by a process of melting, mixing, and pulverizing and classifying, the pulverizing step takes time and productivity decreases. Furthermore, if the method of fixing the toner on the transfer material is a heat roll method or an open method, the fixing temperature must be increased, which goes against energy conservation.

The specific monomer and/or other polymerizable unsaturated monomer of the present invention can be polymerized by solution polymerization, bulk polymerization, or emulsion polymerization.

A dipolymer can be obtained by polymerizing by any method such as suspension polymerization. In this polymerization, the polymerization initiators used include acetyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2.4-dichloroh/diyl peroxide, and perdicarbonate. Diisopropyl, di-2-ethylhexyl perdicarbonate, acetylcyclohexane sulfonyl peroxide, iacetic acid t
ert -butyl, tert-butyl perisobutyrate, azobisisobutyronitrile, 2,2'-azobis-2,4
~dimethylvaleronitrile, per2-ethylhexanoic acid t
Known polymerization initiators such as ert-butyl and tert-butyl perbenzoate are used. These are preferably used in an amount of 0.1 to 15% by weight based on the total amount of polymerizable unsaturated monomers. Moreover, it is preferable to use it by dissolving it in a monomer.

The toner of the present invention contains a colorant and/or magnetic powder.

Coloring agents include carbon black, acetylene black, Hansa Yellow G, cadmium yellow, molybdenum orange, permanent orange, red red iron, rhodamine lake B, first violet B, methyl violet lake, dark blue, phthalocyanine blue, chrome green, pigment green B, Zinc oxide, titanium oxide, nigrosine dye, methylene blue, a-zbengal.

Quinoline Yellow, Ultramarine Blue, Chrome Yellow, Aniline Blue, Calco Oil Blue, Rhodami/6G Lake, Watching Red Barium, Watching Red Strontium.

There are conventionally known pigments or dyes such as malachite green oxalate, DuPont oil red, and mixtures thereof, and these are preferably used in the toner in an amount of 1 to 60% by weight, appropriately selected.

Magnetic powders include metal powders such as iron, manganese, nickel, and cobalt, as well as aluminum and cobalt.

Steel, lead, magnesium, nickel, tin, zinc.

antimony, beryllium, bismuth, cadmium.

Alloys and mixtures of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium, metal oxides such as aluminum oxide, iron oxide, copper oxide, nickel oxide, zinc oxide, titanium oxide, magnesium oxide, chromium oxide or alloys that exhibit ferromagnetism when heat treated.

For example, Heusler alloys such as eva-manganese-copper-aluminum, manganese-copper-tin, etc. can be used. The particle size of the magnetic powder is preferably 10 μm or less.

In particular, the thickness is preferably 1 μm or less. These magnetic powders are contained in the toner in an amount of 30 to 70% by weight. When using magnetic powder, the above-mentioned coloring agent may be further added, and the amount thereof is preferably 10% by weight or less in the toner.

Additives such as a charge control agent can be appropriately added to the toner of the present invention.

As the charge control agent, nigrosine dye, fatty acid-modified nigrosine dye, metal-containing nigrosine dye, metal-containing fatty acid-modified nigrosine dye, tetraalkylammonium halide,
Trialkylammonium (in the formula, 7 represents halogen,
R is an alkylene group having 1 to 3 carbon atoms, n is O or 1
).

A polyamine compound having a structural unit.

A nitrile compound having a structural unit of 10H-C(CN)- (in the formula, the symbol represents hydrogen or an alkyl group having 1 to 3 carbon atoms).

formula (In the formula, R2 represents an alkoxy group or a phenoxy group.

R3 represents hydrogen, an alkoxy group or a phenoxy group), monoalkyltin oxide, dialkyltin oxide, monoaryltin oxide, compound of the formula: (in the formula R; + RS
+ R6 and RJ represent hydrogen, an alkyl group having 1 to 9 carbon atoms, or a substituent having an aromatic ring or a cyclohexene ring, but two or more groups do not represent hydrogen at the same time +
Me represents Cr, Co or Fe; 2M represents hydrogen, potassium, sodium or fatty acid ammonium) Compound 9 formula: (wherein R2 and R6 are an alkylene group having 1 to 9 carbon atoms, an aromatic ring or cyclohexene 1Me represents the ring
and M represent the above-mentioned compound formula 2: (wherein T,
Y and Z represent hydrogen, halogen, carboxyl group, hydroxyl group, nitro group, sulfone group, or sulfonamide group, and 2M and Me are those mentioned above, tetrathiafulvalene, alumina fine powder, etc. can be used; It is usually added to the toner in an amount of 0 to 20% by weight.

Further, when a charge control agent is used, it is preferable to use a light-colored or colorless charge control agent at 9%, which can further prevent printing defects due to adhesion to soft vinyl chloride. Note that the light color refers to the toner that does not use the charge control agent and the toner that does use the charge control agent.

It means that the color difference value measured with a color difference meter is 2 or less. Examples of such charge control agents include tetraalkylammonium halides, trialkylammonium halides, compounds of the formula: (wherein X-几 and n represent the above); A nitrile compound having the structural unit of Formula 1: (in the formula, R and R represent the above).

Monoalkyltin oxide, dialkyltin oxide.

Monoaryltin oxide, compound of the formula: (wherein RS, ed., R≦r&, Me and M are as defined above), formula 2: (wherein R≦e m, Me and M are as defined above) represent)
There are compounds such as

As other additives, a fluidity improver, a cleaning improver, or an anti-offset agent can also be added.

Fluidity improvers provide toner with high fluidity.

It facilitates the continuous supply of toner and forms visible images of good quality. Hydrophobic silica powder is most suitable as the fluidity improver. Such hydrophobic silica powder is made by combining fine powder of silicon dioxide in which the silicon atoms on the surface are silanol groups, for example, octyltrichlorosilane,
Decyltrichlorosilane, nonyltrichlorosilane, 4
-inpropylphenyltrichlorosilane, 4-ter
t-Butylphenyltrichlorosilane, dimethyldichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane.

Dinonyldichlorosilane/Uzidecyldichlorosilane, didodecyldichlorosilane, 4-tart-butylphenyloctyldichlorosilane, dioctyldichlorosilane, didecenyldichlorosilane, dinonenyldichlorosilane, di-2- Ethylhexyldichlorosilane, di-3,
3-Dimethylpentyldichlorosilane 7,t') Methylcumylsilane, trihexylchlorosilane, trioctylcumylsilane, tridecylchlorosilane, dioctylchlorosilane, octyldimethylchlorosilane, 4-isopropylphenyldiethylchlorosilane By reacting with a compound such as K, a hydrophobic group is bonded to the surface silicon atoms of silicon dioxide particles via oxygen atoms.

These hydrophobic silica powders have an average particle size of 1 mμ to
It is preferably within the range of 100 μm.

In particular, it is preferably 2 ffl to 50 μmK. If it is less than 1 mμ, the powder tends to scatter and is difficult to handle, and if it exceeds 100 μm, the photoreceptor is likely to be damaged.

Such hydrophobic silica powders include Aerosil 972,
Silica D-17, R812, RA200H, RX-C (
Above 2 Nippon Aerosil ff) and Taranox 50
0 (manufactured by Tulco), etc.

The toner may be manufactured by blending the hydrophobic silica powder as described above with other toner materials.

In particular, it is preferable to once manufacture a toner using toner materials excluding hydrophobic silica powder, and then add hydrophobic silica powder.

When adding hydrophobic silica powder, hydrophobic silica powder is
0.0 for toner powder without hydrophobic silica powder
Preferably, it is added in an amount of 1 to 15% by weight. In particular, 0.
The amount added is preferably 1 to 10% by weight. This addition amount is 0.
It is less than 0.01% by weight.

The effect of improving fluidity does not appear, and even if it is added in excess of 15% by weight, the effect will not increase accordingly.

A part of the toner component of the cleaning property improving agent adheres to the surface of the photoreceptor or carrier. It prevents the so-called filming phenomenon and always forms clear visible images without fogging even during long-term continuous use.

Cleanability improvers include metal salts of saturated or unsaturated fatty acids such as maleic acid, stearic acid, oleic acid, palmitic acid, and caproic acid.

Linoleic acid, ricinoleic acid or ricylic acid with zinc, magnesium, calcium, cadmium.

Mention may be made of salts with lead, iron, nickel, cobalt, copper or aluminum, with zinc stearate, calcium stearate or magnesium stearate being particularly preferred.

When a cleaning performance improver is used, it is particularly preferable that the cleaning performance improvement agent is added in the same manner as the hydrophobic silica powder described above. The fatty acid metal salt is 0.0% relative to the toner powder not containing the fatty acid metal salt and the hydrophobic silica powder.
It is preferable to add 0.01 to 25% by weight, especially 0.1 to 10% by weight. If the amount is less than 0.01% by weight, the effect of improving cleaning performance will not appear. However, even if it is added in excess of 25% by weight.

It does not increase the effect.

It is generally advantageous to fix a toner image on an image support by a heat fixing method, and this heat fixing method includes a non-contact heat fixing method such as oven fixing, and a contact heating method such as hot roll fixing. However, the contact heating fixing method has high thermal efficiency.
Equipment can be made smaller.

It has advantages such as low power consumption. However, in the contact heat fixing method, when the image support carrying the toner image passes through the heat roll, a part of the toner image is transferred to the heat roll, and after the heat roll has made one revolution, the transferred toner image is transferred to the image support. There is a serious problem of re-metastasis and contamination of the body. The anti-offset agent does not cause offset even in the hot roll fixing method and plays a role in forming high-quality images.

Anti-offset agents include ethylene dipropylene, phthene, pentene, hexene, and heptene.

octene, nonene, decene, 3-methyl-1-butene,
Polymers of olefin monomers such as 3-methyl-2-pentene and 3-propyl-5-methyl-2-hexene, or copolymers of the above-mentioned olefin monomers with acrylic acid, methacrylic acid, vinyl acetate, etc., stearin lower alcohol esters of fatty acids such as butyl acid and propyl stearate, casta wax A (manufactured by Kao Soap),
Polyhydric alcohol esters of fatty acids such as diamond wax (manufactured by Shin Nippon Chemical Co., Ltd.), fatty acids such as Balm Acetate (manufactured by Nippon Oil & Fats Co., Ltd.), Hoechstwax E, Hoechstwax-〇P (manufactured by Hoechst Akchengesellschaft), carnauba wax, etc. higher alcohol ester, bis-amite frustofluoro (Nitto Chemical Industry ■a>, Amide 6)
Alkylene bis fatty acid amide compounds such as L, 78 and 6H (manufactured by Yoken Fine Chemicals), Hoechst Wax C (manufactured by Hoechst Akchengesellschaft).

Zinc stearate, calcium stearate, magnesium stearate, barium stearate.

Fatty acid metal salts such as copper stearate, aluminum stearate, zinc oleate, magnesium oleate, zinc caprylate, magnesium caprylate, zinc linoleate, and calcium linoleate.

Two ball NBI is also 20578, 2007J.

Diene resins and hydroxyl group-containing vinyl resins with a weight average molecular weight of 50,000 or more, such as BR1220.

Examples include carboxyl group-containing vinyl resins.

When an anti-offset agent is added, it is particularly preferred that the anti-offset agent be blended with other toner materials to produce the toner. The anti-offset agent is 0.1 in the toner.
Preferably it is added in an amount of ~50% by weight, especially 1-30% by weight. If the amount is less than 0.1% by weight, the effect of preventing offset will not be exhibited, and even if it is added in excess of 50% by weight, the effect will not increase.

In the present invention, the fluidity improver as described above is used.

The cleaning performance improver and offset inhibitor may be added alone or in combination.

The above-mentioned materials are mixed, for example, in the following manner to produce a toner for developing electrostatic images.

After preliminarily mixing the weighed materials using a W cone, Brengu, Henschel mixer, etc., knead them at a temperature that melts the resin using a pressurized Niegoo, Banbury mixer 2 heat roll, extruder, etc. After cooling, it is coarsely pulverized using a feather mill, pin mill, balberizer, nommer mill, etc. Next, the particles are sieved using an Accucut, Albine classifier, etc., and adjusted to a particle size of preferably 5 to 30 μm.

The toner according to the present invention can be applied to nine different known developing methods.

Furthermore, the toner according to the present invention can be fixed using two different methods.

For example, so-called oil-less and oil-coated heat roll methods,
It can be used in a flash method, an open method, a pressure fixing method, etc., and is particularly suitable for heat roll fixing.

Furthermore, the toner according to the present invention can be used in two different cleaning methods, such as the so-called fur brush method and blade method.

Next, examples of the present invention will be shown.

(1) Synthesis of copolymers a and m 100 parts by weight of toluene and a mixed solution of monomers and benzoyl peroxide having the composition shown in Table 1 were placed in a reaction vessel at 90%
After keeping the temperature at 110°C for 3 hours, the temperature was raised to 110°C and held for 10 hours. Next, toluene was removed in a vacuum dryer to obtain a copolymer. The glass transition temperature of the obtained copolymer is shown in Table IK.

(2) Production of toner, Examples 1 to J/f The materials shown in Table 2 were premixed in a Henschel mixer, and then melted and kneaded in a kneader. Next, the cooled mixture was finely pulverized using a pin mill and a jet mill, and classified into 9 parts to give an average particle size of 10 to 1.
A toner of 5 μm was obtained.

(3) Evaluation method Examples 1 to 6 and 9 to 15 8F-750 (Sharp ■
NP-200J for Examples 7 and 8.
A print was made using a copying machine manufactured by Canon (Canon ■, however, transfer to paper was performed by applying a negative voltage and using a two-reversal development method). The obtained print was mixed with 25 dioctyl 7-talate.
Sandwiched between soft PVC polymer sheets containing % by weight and heated to 30% by weight
℃, a load of 59 f/Cm'', and a test time of 1800 hours to examine the adhesion of printed characters to the soft vinyl chloride polymer sheet.

Hereinafter, Example 16 A toner in which 0.1% Tallanox 500 was externally added to 100 parts by weight of the toner of Example 1 was evaluated in the same manner as in Example 1. I was not able to admit.

All of the prints obtained in Examples had image densities of 1.2 or higher and capri of white areas of 0.8 or lower.

9 Image density and Capri values are measured using a Macbeth reflection densitometer (
This is the optical reflection density measured by Macbeth Co., Ltd.).

Comparative Example 1 When copolymer a in Example 1 was replaced with a styrene-butyl methacrylate (70/30 weight ratio) copolymer, printing defects caused by adhesion to a soft PVC polymer sheet were observed. It was illegible.

(Effects of the Invention) As is clear from the above results, the toner for developing electrostatic images according to the present invention has good image density and capri resistance,
Shows excellent adhesion resistance to soft PVC polymers.

I 'z・go--

Claims (1)

[Claims] 1. At least one polymerizable unsaturated monomer represented by any of the following general formulas I to V as a component.
A toner for developing electrostatic images comprising 90% by weight of a polymer as a binder. I ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ III ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ IV ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ V ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ [However, in general formulas I to V, R_1 is hydrogen or a methyl group, R_2 is an alkylene group having 1 to 6 carbon atoms, R_3, R_4, R_5, R_6, R_7, R_8,
R_9 and R_1_0 are hydrogen, an alkylene group having 1 to 3 carbon atoms, or a halogen, and these may be the same or different, and R_1_1 is CH_2, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
CH_2CH_2 or]